KR20060076297A - Method of regenerating deteriorated catalyst - Google Patents

Method of regenerating deteriorated catalyst Download PDF

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KR20060076297A
KR20060076297A KR1020067005185A KR20067005185A KR20060076297A KR 20060076297 A KR20060076297 A KR 20060076297A KR 1020067005185 A KR1020067005185 A KR 1020067005185A KR 20067005185 A KR20067005185 A KR 20067005185A KR 20060076297 A KR20060076297 A KR 20060076297A
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catalyst
tungsten
vanadium
deteriorated
regenerating
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KR101096985B1 (en
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노부오 마츠모토
데츠오 고다마
아츠시 후쿠쥬
마사요시 이치키
가즈히로 야노
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히다치 조센 가부시키가이샤
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten

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Abstract

A method of regenerating a deteriorated denitrification catalyst by an easy and simple procedure. A catalyst which is for use in the reductional removal of NOx contained in a waste gas with ammonia as a reducing agent and has deteriorated in activity due to long-term use is washed with an aqueous acid solution containing vanadium and/or tungsten and having a pH of 4 or lower, preferably 2 or lower. This washing mainly dissolves away alkali metals, alkaline earth metals, arsenic, and sulfur, which are deteriorating ingredients, and the vanadium and tungsten which have deteriorated in activity. Simultaneously therewith, the vanadium and/or tungsten as an active ingredient is deposited. Examples of the alkali metals include potassium and sodium, while examples of the alkaline earth metals include calcium.

Description

열화 촉매의 재생 방법{METHOD OF REGENERATING DETERIORATED CATALYST}Regeneration method of deterioration catalyst {METHOD OF REGENERATING DETERIORATED CATALYST}

본 발명은 배기 가스 중의 질소화물을 암모니아 환원제를 이용하여 접촉 환원하는 탈초 촉매(denitration catalyst)로서 열화된 것의 재생 방법에 관한 것이다. 열화된 탈초 촉매는 석탄 연소 배기 가스 등의 오염 배기 가스 중에서 사용된 것, 가스 터빈 배기 가스 등의 청정 배기 가스 중에서 사용된 것을 포함한다.The present invention relates to a method for regenerating a deteriorated as a denitration catalyst for catalytically reducing a nitride in exhaust gas with an ammonia reducing agent. Deteriorated denitration catalysts include those used in contaminated exhaust gases such as coal combustion exhaust gases and those used in clean exhaust gases such as gas turbine exhaust gases.

종래, 열화된 탈초 촉매의 재생법은 많이 제안되어 있다(일본 특허 제2994769호 공보, 일본 특허 공개 평성 제11-057410호 공보, 일본 특허 공개 제2000-037634호 공보, 일본 특허 공개 제2000-037635호 공보, 일본 특허 공개 평성 제10-235209호 공보, 일본 특허 공개 평성 제10-066875호 공보, 일본 특허 공개 평성 제7-222924호 공보, 일본 특허 공개 평성 제6-099164호 공보, 일본 특허 공개 평성 제10-337483호 공보, 일본 특허 공개 평성 제10-156193호 공보, 일본 특허 공개 평성 제10-156192호 공보, 일본 특허 공개 제2000-107612호 공보, 일본 특허 공개 제2000-102737호 공보 참조). 이들 방법 중에서, 열화 촉매를 알칼리 수용액으로 세정하여 활성 성분을 재담지하여 재생하는 방법, 열화 촉매를 산 수용액으로 세정하여 활성 성분을 재담지하여 재생하는 방법, 열화 촉매를 알칼리 수용액으로 세정하고 이어서 산 수용액으로 세정하며, 그 후, 활성 성분을 재담지하여 재생하 는 방법 등이 있다.Conventionally, many methods for regenerating deteriorated denitration catalysts have been proposed (Japanese Patent No. 2994769, Japanese Patent Application Laid-Open No. 11-057410, Japanese Patent Laid-Open No. 2000-037634, and Japanese Patent Laid-Open No. 2000-037635). Japanese Patent Application Laid-Open No. 10-235209, Japanese Patent Application Laid-Open No. 10-066875, Japanese Patent Application Laid-Open No. 7-222924, Japanese Patent Application Laid-Open No. 6-099164, Japanese Patent Publication See JP-A-10-337483, JP-A-10-156193, JP-A-10-156192, JP-A-2000-107612, and JP-A-2000-102737. ). Among these methods, a method of washing a deterioration catalyst with an aqueous alkali solution to re-support and regenerate the active ingredient, a method of washing a deterioration catalyst with an aqueous acid solution to re-support the active ingredient for regeneration, and a method of washing the deterioration catalyst with an aqueous alkali solution followed by acid Washing with an aqueous solution, and then re-supporting and regenerating the active ingredient.

탈초 촉매가 석탄 연소 배기 가스나 가스 터빈 배기 가스 등의 처리에 장기간 사용되면, 배기 가스 중이나 재(ash) 속에 함유되는 열화 성분 칼슘, 칼륨, 나트륨, 비소, 유황 등에 의해 활성 열화를 일으키고, 또한, 활성 성분인 바나듐, 텅스텐이 열적 응집 등에 의해 활성 열화를 일으킨다. 상기 제안된 재생 방법, 즉, 열화 촉매를 알칼리 수용액으로 세정하여 활성 성분을 재담지하여 재생하는 방법, 산 수용액으로 세정하여 활성 성분을 재담지하여 재생하는 방법, 알칼리 수용액 이어서 산 수용액으로 세정한 후 활성 성분을 재담지하여 재생하는 방법에서는, 모두 세정에 따라 활성 성분도 용출되기 때문에, 활성 성분의 재담지가 필요하게 되어, Z정 처리와 활성 성분의 재담지 처리의 공정을 나누어 행할 필요가 있었다. 그 때문에, 처리 공정이나 액 관리가 복잡해지고, 폐액량이 증대하여 비용 상승 등을 초래하는 문제가 있었다.When the denitration catalyst is used for a long time for the treatment of coal combustion exhaust gas or gas turbine exhaust gas, active deterioration is caused by deterioration components calcium, potassium, sodium, arsenic, sulfur, etc. contained in the exhaust gas or ash, Active ingredients vanadium and tungsten cause active deterioration by thermal agglomeration or the like. The proposed regeneration method, that is, a method of regenerating the active catalyst by washing the degradation catalyst with an aqueous alkali solution, reloading the active ingredient by washing with an acid aqueous solution, after washing with an aqueous alkali solution followed by an aqueous acid solution In the method of re-supporting and regenerating the active ingredient, the active ingredient is also eluted with washing, and thus, the reloading of the active ingredient is required, and the steps of the Z tablet treatment and the reloading treatment of the active ingredient have to be divided. Therefore, there is a problem that the treatment process and the liquid management are complicated, and the amount of the waste liquid increases, resulting in a cost increase.

본 발명은 상기 문제에 대하여 간편하고 또한 단순한 방법으로 열화된 탈초 촉매를 재생하는 방법을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a method for regenerating a denitration catalyst deteriorated in a simple and simple manner to the above problem.

본 발명자들은 상기 문제를 해결하기 위해서 이하의 것을 착안하였다. (1) 산 또는 알칼리 세정만의 재생 방법에서는 촉매 성분이 용출되고, 성능이 완전히 회복되지 않기 때문에, 활성 성분의 재담지가 필요하게 된다.MEANS TO SOLVE THE PROBLEM The present inventors devised the following in order to solve the said problem. (1) In the regeneration method only for acid or alkali washing, the catalyst component is eluted and the performance is not completely recovered. Therefore, the reloading of the active ingredient is necessary.

(2) 바나듐 및/또는 텅스텐을 함유하는 수용액은 넓은 pH 영역에서 안정하다.(2) An aqueous solution containing vanadium and / or tungsten is stable in a wide pH range.

이 사실에 착안하여 열화 촉매를 바나듐 및/또는 텅스텐을 함유하는 산 수용액으로 세정함으로써, 또는 바나듐 및/또는 텅스텐을 함유하는 알칼리 수용액으로 세정함으로써, 촉매 중에 축적된 열화 성분이나 활성 열화된 바나듐이나 텅스텐을 용출하는 동시에, 활성 성분인 바나듐 및/또는 텅스텐을 재담지할 수 있는 간편하고 또한 단순한 재생 방법을 완성하기에 이르렀다. 바나듐 및/또는 텅스텐을 함유하는 산 수용액으로 세정하는 재생 방법은, 주로 열화 인자가 알칼리에 의한 촉매에 적용하면 보다 효과적이다. 또한, 바나듐 및/또는 텅스텐을 함유하는 알칼리 수용액으로 열화 촉매를 세정하는 재생 방법은, 주로 열화 인자가 비소에 의한 촉매에 적용하면 보다 효과적이다.In view of this fact, the deterioration component accumulated in the catalyst or active deteriorated vanadium or tungsten by washing the deterioration catalyst with an aqueous acid solution containing vanadium and / or tungsten or with an aqueous alkali solution containing vanadium and / or tungsten While eluting the solution, a simple and simple regeneration method capable of resupporting the active ingredients vanadium and / or tungsten has been completed. The regeneration method of washing with an aqueous acid solution containing vanadium and / or tungsten is more effective when the deterioration factor is mainly applied to the catalyst by alkali. Moreover, the regeneration method of washing a deterioration catalyst with the aqueous alkali solution containing vanadium and / or tungsten is more effective when a deterioration factor is mainly applied to the catalyst by arsenic.

본 발명에 따른 제1의 것은, 환원제로서 암모니아를 이용하여 폐가스 중의 NOx를 환원 제거하는 방법에 사용되는 촉매로서, 장기간 사용함으로써 활성 저하된 촉매를 바나듐 및/또는 텅스텐을 함유하는 pH 4 이하, 바람직하게는 pH 2 이하의 산 수용액으로 세정함으로써, 주로 열화 성분인 알칼리 금속, 알칼리 토류 금속, 비소, 유황, 활성 열화된 바나듐, 텅스텐을 용출하는 동시에, 활성 성분인 바나듐 및/또는 텅스텐을 담지하는 것을 특징으로 하는 열화 촉매의 재생 방법이다. 알칼리 금속은 칼륨, 나트륨 등이며, 알칼리 토류 금속은 칼슘 등이다.The first one according to the present invention is a catalyst used in a method for reducing and removing NOx in waste gas by using ammonia as a reducing agent, wherein a catalyst deactivated by long-term use contains vanadium and / or tungsten at a pH of 4 or less, preferably Preferably, by washing with an aqueous acid solution of pH 2 or less, it is possible to elute mainly alkali metals, alkaline earth metals, arsenic, sulfur, active deteriorated vanadium and tungsten, and to carry vanadium and / or tungsten as active ingredients. It is a regeneration method of the deterioration catalyst characterized by the above-mentioned. Alkali metals are potassium, sodium, and the like, and alkaline earth metals are calcium and the like.

제1 발명에 있어서, 산으로서는 질산, 염산 및/또는 황산을 이용하는 것이 바람직하다.In the first invention, it is preferable to use nitric acid, hydrochloric acid and / or sulfuric acid as the acid.

본 발명에 따른 제2의 것은, 환원제로서 암모니아를 이용하여 폐가스 중의 NOx를 환원 제거하는 방법에 사용되는 촉매로서, 장기간 사용함으로써 활성 저하된 촉매를 바나듐 및/또는 텅스텐을 함유하는 pH 8 이상, 바람직하게는 pH 10 이상의 알칼리 수용액으로 세정함으로써, 주로 열화 성분인 알칼리 금속, 비소, 유황, 활성 열화된 바나듐, 텅스텐을 용출하는 동시에, 활성 성분인 바나듐 및/또는 텅스텐을 담지하는 것을 특징으로 하는 열화 촉매의 재생 방법이다. 알칼리 금속은 칼륨, 나트륨 등이다.The second one according to the present invention is a catalyst used in a method for reducing and removing NOx in waste gas by using ammonia as a reducing agent, wherein the catalyst deactivated by long-term use contains a vanadium and / or tungsten at a pH of 8 or higher, preferably Preferably, the deterioration catalyst is characterized by eluting alkali metals, arsenic, sulfur, active deteriorated vanadium and tungsten as the main components by washing with an aqueous alkali solution of pH 10 or higher, and carrying vanadium and / or tungsten as active components. How to play. Alkali metals are potassium, sodium and the like.

제2 발명에 있어서, 알칼리 수용액으로서는 암모니아수를 이용하는 것이 바람직하다.In 2nd invention, it is preferable to use ammonia water as aqueous alkali solution.

본 발명에 따르면, 1회의 침지 처리라는 간편하고 또한 단순한 방법으로 열화 탈초 촉매를 재생시킬 수 있다.According to the present invention, the deterioration denitration catalyst can be regenerated by a simple and simple method of one immersion treatment.

도 1은 실시예 1과 비교예 1의 각 재생 촉매의 재생 전후의 성능을 나타낸 그래프.1 is a graph showing the performance before and after regeneration of each regeneration catalyst of Example 1 and Comparative Example 1.

도 2는 실시예 2와 비교예 2의 각 재생 촉매의 재생 전후의 성능을 나타낸 그래프.2 is a graph showing the performance before and after regeneration of each regeneration catalyst of Example 2 and Comparative Example 2.

다음으로, 본 발명을 구체적으로 설명하기 위해서, 본 발명의 실시예 및 이것과의 비교를 나타내기 위한 비교예를 몇 가지 든다.Next, in order to demonstrate this invention concretely, several comparative examples for showing the Example of this invention and a comparison with this are given.

실시예 1Example 1

(1) 탈초 성능(1) denitration performance

촉매의 성능은 탈초 반응이 NOx의 1차 반응이라고 가정하고, NOx/NH3 비=1.0에 있어서의 반응 속도 정수 "K"[K=-(AV)ln(1-x), AV는 촉매의 기하 표면적당 배기 가스량, x: 탈초율]와, 열화 처치를 강구하지 않은 초기의 반응 속도 정수 "K0"와의 비 "K/K0"로서 정의한다. 따라서, 초기 상태에서는 K/K0=1이다.The performance of the catalyst assumes that the denitrification reaction is the primary reaction of NOx, and the reaction rate constant "K" [K =-(AV) ln (1-x) at NOx / NH 3 ratio = 1.0, where AV Exhaust gas amount per geometric surface area, x: denitrification rate] and the ratio "K / K 0 " to the initial reaction rate constant "K 0 " without deterioration treatment. Therefore, K / K 0 = 1 in the initial state.

(2) 실열화 탈초 촉매의 재생(2) Regeneration of the deteriorated denitration catalyst

장기간 석탄 연소 가스 탈초에 사용하여 성능이 저하된 촉매에 대해서 활성 측정을 행하였다. 다음으로, 질산 수용액에 메타바나딘산암모늄(NH4VO3)을 0.03 mol/ℓ 농도가 되도록 첨가한 수용액(pH 1.2)을 조제하고, 거기에 상기 성능 저하 촉매를 5 시간 침지하였다. 침지 후에는 250℃에서 1 시간 소성을 행하여, 성능의 회복성을 측정하였다. 그 결과를 도 1에 나타낸다. 이 1회의 처리 조작으로 성능은 거의 초기 성능까지 회복되었다.Activity measurement was performed about the catalyst whose performance was degraded by using for long-term coal combustion gas denitrification. Next, an aqueous solution (pH 1.2) obtained by adding ammonium metavanadate (NH 4 VO 3 ) to a concentration of 0.03 mol / L in an aqueous nitric acid solution was prepared, and the performance degradation catalyst was immersed therein for 5 hours. After immersion, baking was performed at 250 degreeC for 1 hour, and the recoverability of performance was measured. The result is shown in FIG. In this one-time processing operation, performance was restored to almost initial performance.

실시예 2Example 2

비소 열화 촉매의 재생Regeneration of Arsenic Degradation Catalyst

탈초 촉매를 As로 하여 약 25 ppm의 비소 산화물 증기를 함유하는 공기에 350℃에서 4 시간 노출시켜 성능을 열화시켜, 모의 비소 열화 촉매를 조제하였다. NH3수에 메타바나딘산암모늄(NH4VO3)을 0.03 mol/ℓ, WO3을 0.5 mol/ℓ의 농도가 되도록 각각 첨가한 수용액(pH 10.2)을 조제하고, 거기에 상기 비소 열화 촉매를 5 시간 침지하였다. 침지 후에는 400℃에서 1 시간 소성을 행하여, 성능의 회복성을 측정하였다. 이 결과를 도 2에 나타낸다. 이 1회의 처리 조작으로 성능은 거의 초기 성능까지 회복되었다.The denitration catalyst was used as As and exposed to air containing about 25 ppm of arsenic oxide vapor at 350 DEG C for 4 hours to deteriorate the performance, thereby preparing a simulated arsenic deterioration catalyst. The NH 3 can metavanadate, ammonium (NH 4 VO 3) to 0.03 mol / ℓ, the WO 3 to prepare an aqueous solution (pH 10.2) which were added to a concentration of 0.5 mol / ℓ, there is the arsenic deteriorated catalyst to Was soaked for 5 hours. After immersion, baking was performed at 400 degreeC for 1 hour, and the recoverability of performance was measured. This result is shown in FIG. In this one-time processing operation, performance was restored to almost initial performance.

비교예 1Comparative Example 1

실열화 탈초 촉매의 재생:Regeneration of the depyrolytic denitrification catalyst:

실시예 1의 (2) 실열화 탈초 촉매의 재생 공정에 있어서, 메타바나딘산암모늄을 함유하지 않은 질산 수용액(pH 1.2)을 이용하여 침지를 행한 것 이외에는, 상기 공정과 동일한 조작을 행하였다. 그 결과를 도 1에 나타낸다. 질산 수용액(pH 1.2)만의 처리 조작에서는, 처리시에 활성 성분이 용출되어 버리기 때문에, 활성은 초기 성능까지 회복되지 않았다.In the regeneration step of the deterioration denitration catalyst of Example 1, the same operation as in the above step was carried out except that immersion was performed using an aqueous solution of nitric acid (pH 1.2) containing no ammonium metavanadate. The result is shown in FIG. In the treatment operation only with aqueous nitric acid solution (pH 1.2), since the active ingredient eluted at the time of treatment, the activity did not recover to the initial performance.

비교예 2Comparative Example 2

실열화 탈초 촉매의 재생Regeneration of the deterioration denitrification catalyst

실시예 2에 있어서, 메타바나딘산암모늄도 WO3도 함유하지 않은 NH3 수용액(pH 10.2)을 이용하여 침지를 행한 것 이외에는, 실시예 2와 동일한 조작을 행하였다. 그 결과만으로 침지하는 것 이외에는, 동일한 방법으로 행하였다. 결과를 도 2에 나타낸다. NH3 수용액(pH 10.2)만의 처리 조작에서는, 처리시에 활성 성분이 용출되어 버리기 때문에, 성능은 초기 성능까지 회복되지 않았다.In Example 2, operation similar to Example 2 was performed except having been immersed using aqueous NH 3 solution (pH 10.2) containing neither ammonium metavanadate nor WO 3 . It carried out by the same method except having immersed only in the result. The results are shown in FIG. In the treatment operation of only NH 3 aqueous solution (pH 10.2), since the active ingredient eluted at the time of treatment, the performance did not recover to the initial performance.

본 발명은 배기 가스 중의 질소 산화물을 암모니아 환원제를 이용하여 접촉 환원하는 탈초 촉매로서 열화된 것의 재생 방법을 제공한다. 본 발명 방법에 따르 면, 1회의 침지 처리라는 간편하고 또한 단순한 방법으로 열화 탈초 촉매를 재생시킬 수 있다.The present invention provides a method for regenerating the deteriorated catalyst as a denitration catalyst for catalytically reducing nitrogen oxides in the exhaust gas using an ammonia reducing agent. According to the method of the present invention, the denitration catalyst can be regenerated by a simple and simple method of one soaking treatment.

Claims (4)

환원제로서 암모니아를 이용하여 폐가스 중의 NOx를 환원 제거하는 방법에 사용되는 촉매로서, 장기간 사용함으로써 활성 저하된 촉매를, 바나듐 및/또는 텅스텐을 함유하는 pH 4 이하의 산 수용액으로 세정함으로써, 주로 열화 성분인 알칼리 금속, 알칼리 토류 금속, 비소, 유황, 활성 열화된 바나듐, 텅스텐을 용출하는 동시에, 활성 성분인 바나듐 및/또는 텅스텐을 담지하는 것을 특징으로 하는 열화 촉매의 재생 방법.A catalyst used in a method of reducing and removing NOx in waste gas by using ammonia as a reducing agent, wherein the catalyst that has been deactivated after long-term use is washed with an aqueous acid solution having a pH of 4 or less containing vanadium and / or tungsten. A method for regenerating a deterioration catalyst characterized by eluting phosphorus alkali metal, alkaline earth metal, arsenic, sulfur, active deteriorated vanadium and tungsten, and carrying vanadium and / or tungsten as active ingredients. 제1항에 있어서, 산으로서 질산, 염산 및/또는 황산을 이용하는 것을 특징으로 하는 열화 촉매의 재생 방법.The method for regenerating a deterioration catalyst according to claim 1, wherein nitric acid, hydrochloric acid and / or sulfuric acid are used as the acid. 환원제로서 암모니아를 이용하여 폐가스 중의 NOx를 환원 제거하는 방법에 사용되는 촉매로서, 장기간 사용함으로써 활성 저하된 촉매를, 바나듐 및/또는 텅스텐을 함유하는 pH 8 이상의 알칼리 수용액으로 세정함으로써, 주로 열화 성분인 알칼리 금속, 비소, 유황, 활성 열화된 바나듐, 텅스텐을 용출하는 동시에, 활성 성분인 바나듐 및/또는 텅스텐을 담지하는 것을 특징으로 하는 열화 촉매의 재생 방법.A catalyst used in a method of reducing and removing NOx in waste gas by using ammonia as a reducing agent.A catalyst that is deactivated after long-term use is washed with an aqueous alkali solution having a pH of 8 or higher containing vanadium and / or tungsten. A method for regenerating a deterioration catalyst characterized by eluting an alkali metal, arsenic, sulfur, active deteriorated vanadium and tungsten, and carrying vanadium and / or tungsten as active ingredients. 제3항에 있어서, 알칼리 수용액으로서 암모니아수를 이용하는 것을 특징으로 하는 열화 촉매의 재생 방법.The method for regenerating a deterioration catalyst according to claim 3, wherein ammonia water is used as aqueous alkali solution.
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